CN104237178A - Method and device for detecting trace metal elements in water body by using laser-induced breakdown spectroscopy assisted by direct current discharging vaporization - Google Patents
Method and device for detecting trace metal elements in water body by using laser-induced breakdown spectroscopy assisted by direct current discharging vaporization Download PDFInfo
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Abstract
The invention discloses a method and a device for detecting trace metal elements in a water body by using the laser-induced breakdown spectroscopy assisted by direct current discharging vaporization. High voltage direct current discharging is utilized to vaporize a liquid sample, the vaporized sample is separated through a separation device, gas is injected to a graphite bearing piece, the graphite bearing piece containing elements to be detected is subjected to pulse laser ablation induction to generate plasma and transmit spectroscopy signals, and finally a spectrograph is utilized to conduct detection analysis to measure the trace metal in the water body. By means of the method and the device, the pulse laser sample ablation efficiency is greatly improved, the detected spectroscopy signals are greatly strengthened, the detection sensitivity is improved, the detection limit of the metal elements is reduced, and the method is feasible for online high-efficiency quick detection of the metal elements in the water body.
Description
Technical field:
The present invention relates to laser diagnostics and spectral measurement analysis field, especially for apparatus and method for the quick detection to Heavy Metals in Waters metal, this technology can detect metallic element in industrial waste water, sanitary sewage, food, medicine online fast and efficiently.
Background technology:
Current water pollution becomes global problem, and have a strong impact on children and the healthy and even life security of adult, if human body absorbs too much molybdenum element can cause gout sample syndrome, arthralgia and deformity, compromised kidneys, and have growth retardation, artery sclerosis, the illnesss such as connective tissue sex change.Heavy metal Hg is savings property poisonous substance, and except chronic and acute poisoning, also have carcinogenic and mutagenesis, namely Japanese minamata disease is caused by methyl mercury accumulates in people and animals' brain.After cadmium enters human body, form cadmium albumen in vivo, arrive whole body by blood circulation, and put aside selectively in target organ-kidney, liver.The harm major embodiment of chromium is intoxicating effect, spread effect, cumulative function, allergic reaction, carcinogenesis and mutagenesis, maximum to the harm of neurocyte.In order to effectively prevent and reduce heavy metal to human body and biological harm, preserve the ecological environment, we must strengthen the examination and controlling of heavy metal element.At present, the method that heavy metal carries out detecting mainly contains spectrophotometric method, volt-ampere leaching, atomic absorption spectrography (AAS), fluorescent spectrometry and mass spectroscopy.In order to meet the needs that on-line continuous detects, be badly in need of finding the detection method that a kind of highly sensitive, fast and easy, multielement detect simultaneously.
LIBS (Laser-Induced Breakdown Spectroscopy, LIBS) is a kind of brand-new material element analytical approach.LIBS technology has the sample pretreatment without the need to complexity, contactless Non-Destructive Testing, express-analysis, multielement real-time online detects, do not need the features such as vacuum, can be used for metal material and nonconducting nonmetallic materials (as plastics, the pottery) constituent analysis of conduction, be with a wide range of applications in fields such as environmental pollution, archaeology, metallurgy, survey of deep space and medical science.But use LIBS still higher to the detection limit of Water body metallic element at present, the requirement that some field is detected cannot be met.When adopting LIBS to detect fluid sample, method conventional at present adopts hydrofluidic to detect, find in experiment, liquid excites the excitation threshold producing plasma usually larger, and the less stable of signal detected in an experiment, its maximum shortcoming is that the detection limit of heavy metal element is higher, and these all constrain the practical application that LIBS detects fluid sample.
Summary of the invention:
The object of the invention is to liquid cathode glow discharge technique to combine with LIBS, reduce the breakdown threshold of LIBS, improve detection sensitivity, reduce detection limit, meet the actual requirement that metallic element is detected.Fluid sample is converted into gas by high voltage direct current charging method by the present invention, then is separated raising metallic element concentration to be measured through gas-liquid separation device, detects finally by LIBS.Because in gaseous sample, metallic element density is little, when puncturing in atmosphere, easily be excited, breakdown threshold can reduce, ablation efficiency also can be greatly improved, because ablation breakdown process is carried out in atmosphere, suffered environmental pressure will be far smaller than pressure in liquid environment, so the life-span of plasma is also extended, atomic emission spectrum is conducive to be separated from the noise spectrum such as continuous radiation and bremsstrahlung, and then raising detection sensitivity, strengthen signal intensity.
Pick-up unit of the present invention, mainly comprises peristaltic pump, direct-current discharge device, high-voltage DC power supply, carrier gas feeding mechanism, gas-liquid separator, micro pump, gas buffer room, assembles quartz lens, Nd:YAG pulsed laser, coupling fiber equipment, optical fiber, spectrometer, enhancement mode charge coupled cell (ICCD), computing machine.Peristaltic pump stably injects fluid sample, direct-current discharge device carries out electric discharge to fluid sample and produces high-temperature steam, carrier gas delivery sample vapors enters the cooling of gas-liquid separator back warp cold water, part water vapor is separated, gas enters surge chamber stabilizing gas flow velocity, gas is ejected on graphite flake, graphite flake excites through pulse laser ablation and produces plasma and launch spectral signal, light splitting and detection are carried out to the light signal collected, eventually through software analysis output spectrum information by the spectrometer of band ICCD.
Another object of the present invention is to provide a kind of method that metallic element detects.
Realizing the technical scheme that the object of the invention adopts is:
Direct-current discharge vaporization auxiliary laser induced breakdown spectroscopy detects the method for trace-metal in water body.The method is: be first stably transported to by sample solution in direct-current discharge device, by high-voltage DC power supply, fluid sample is discharged, its voltage is 900V ~ 1400V, discharge current is 50mA ~ 110mA, electrode separation is 1mm ~ 6mm, fluid sample is made to gasify as high-temperature steam, high-temperature gas is transported in gas-liquid separator by carrier gas, high-temperature gas through condensate water cooling be separated, part water vapor is separated, metallic element concentration to be measured is improved, gas containing metallic element to be measured enters gas buffer room stabilizing gas flow velocity, the nozzle that gaseous sample is 0.2 ~ 2mm through internal diameter is ejected on graphite flake, the angle on airflow direction and graphite flake surface is 30 ~ 60 °.The pulse laser focused on through convergent lens excites generation plasma to gas eject position irradiation on meta anthracite and launches spectral signal, the light signal of gathering-device plasma is collected, detected by ICCD by spectrometer light splitting, finally export by analysis software the spectral signal detected, realize the detection to trace metal element in water body.
Accompanying drawing illustrates:
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1 is the apparatus structure schematic diagram that direct-current discharge of the present invention vaporization auxiliary laser induced breakdown spectroscopy detects trace-metal in water body, wherein 1,2 is peristaltic pump, 3 is direct-current discharge device, 4 is high-voltage DC power supply, 5 carrier gas feeding mechanisms, 6 is gas-liquid separator, and 7 is micro pump, and 8 is gas buffer room, 9 is Nd:YAG pulsed laser, 10 for assembling quartz lens, and 11 is graphite flake, 12 fiber coupling devices, 13 is optical fiber, 14 is spectrometer, and 15 is the charge-coupled image sensor (ICCD) of enhancement mode, and 16 is computing machine.
Fig. 2 is direct-current discharge apparatus structure schematic diagram, and wherein 16 is electric discharge pond, and 17 is metal anode, and 18 is electrode separation adjusting knob, 19 is negative electrode, and 20 is inlet nozzle, and 21 is waste liquid outlet, and 22 is carrier gas inlet, 23 is gaseous sample outlet, and 24 is porcelain tube resistance, and 25 is high-voltage DC power supply.
Fig. 3 is gas-liquid separation device structural representation, and wherein 26 is air intake opening, and 27 is freeing port, 28 water inlets, and 29 is water delivering orifice, and 30 is gas outlet.
Fig. 4 is gas buffer cell structure schematic diagram, and wherein 31 is sealed glass jars, and 32 is injection port, and 33 is outlet.
Fig. 5 is excitation device schematic diagram, and wherein 34 is laser beam, and 35 is convergent lens, and 36 is nozzle, and 37 is fiber coupler, and 38 is graphite flake.
Fig. 6 is HgCl
2solution concentration is respectively 1000 μ g/L, 500 μ g/L, 100 μ g/L, the spectrogram of 50 μ g/L, A:Hg atom 253.65nm characteristic spectral line.
Embodiment:
Referring now to accompanying drawing, one embodiment of the present of invention are described.
Inventor completes following experiments, and the contrive equipment described in employing is to HgCl
2hg element in solution detects.
First, by peristaltic pump 1, the sample solution in sample bottle is transported in direct-current discharge device 3, peristaltic pump 1 flow velocity is 8.7mL/min, electric discharge device 3 negative electrode 19 is connected with the negative pole of high-voltage DC power supply 25 after current-limiting resistance 24 (2.7k Ω), (diameter is 2mm for high-voltage DC power supply 25 positive pole and solid tungsten bar, end becomes 15 ° of cone angles) anode 17 is connected, and concrete on-link mode (OLM) is as shown in Figure 2.In experiment, 1200V voltage is applied between liquid cathode 19 and tungsten bar anode 17, the air of two interpolars can be breakdown, produce atmospheric pressure plasma, meanwhile fluid sample is vaporized as high-temperature steam, regulate electrode separation by electrode separation adjusting knob 18, make discharge current be 80mA, the waste liquid produced after electric discharge is got rid of through peristaltic pump 2.Carrier gas feeding mechanism 5 provides carrier gas (air) to be sent to by high-temperature steam in gas-liquid separator 6, Fig. 3 gives the concrete structure of gas-liquid separator 6, gas enters gas-liquid separation device from air intake opening 26, simultaneously cold water is input to device from water inlet 28 by micro pump, finally export from water delivering orifice 29, the flow velocity of micro pump 7 is 0.75L/min, cooled by cold water during the interior pipe of gaseous sample by gas-liquid separator, part water vapor in gas is separated from freeing port 27 and flows out, and the gas after being separated is exported by gas outlet 30.
In order to make the gas flow rate after process stablize, be passed in gas buffer room 8 by the gas after being separated, as shown in Figure 4, gas is inputted by injection port 32 concrete structure of gas buffer room, exports from outlet 33.
The nozzle 36 that the gas exported from gas buffer room 8 is 2mm by internal diameter sprays, and ejection air-flow and graphite flake 38 surface are in 45 °.Nd:YAG pulsed laser 9 Output of laser 34 of 1064nm wavelength carries out ablation to gas eject position on meta anthracite after convergent lens 35 focuses on, laser single-pulse energy is 16mJ, excite and produce plasma and launch spectral signal, then collected by gathering-device 10 and 12 and be delivered to spectrometer 14 by optical fiber 13, after spectrometer 14 light splitting, (gain is 500 to detect output through ICCD detector 15 again, time delay is 0.7 μ s, gate-width is 10 μ s), last by analysis software process, by computing machine 16 output spectrum information.Fig. 6 is the variable concentrations HgCl adopting this contrive equipment to detect
2hg solution atom 253.65nm characteristic spectral line intensity.
Claims (10)
1. direct-current discharge vaporization auxiliary laser induced breakdown spectroscopy detects the method for metallic element in water body, it is characterized in that: first stably inject fluid sample, uses direct-current discharge device to carry out electric discharge to fluid sample and makes fluid sample become gas.Containing the gas of element to be measured through gas-liquid separator separates, gas after being separated is ejected on graphite flake, the steam be sprayed on around graphite flake is excited by laser-induced breakdown device, produce plasma emission spectroscopy signal, finally by spectrum detection device, spectral signal is analyzed, thus realize the detection to trace metal element in water body.
2. direct-current discharge vaporization auxiliary laser induced breakdown spectroscopy according to claim 1 detects the method for trace metal element in water body, it is characterized in that, liquid cathode glow discharge device is used to make it become gaseous state from liquid state to sample electric discharge, detected by LIBS again, realize the detection to metallic element in water body.
3. direct-current discharge vaporization auxiliary laser induced breakdown spectroscopy according to claim 1 detects the method for trace metal element in water body, it is characterized in that, improves metallic element concentration to be measured in gas by gas-liquid separator.
4. the pick-up unit designed of detection method according to claim 1, the feature of this device is: the peristaltic pump that this device Negotiation speed is adjustable stably injects fluid sample, high-voltage DC power supply provides voltage for electric discharge device, using metal as anode, using liquid as negative electrode, electric discharge is carried out to fluid sample and produces high-temperature steam, the waste liquid produced after electric discharge exports through peristaltic pump, carrier gas delivery sample vapors enters gas-liquid separator, micro pump injects cold water to gas-liquid separator and carrys out cooling down high-temperature steam, part water vapor is separated, gas enters surge chamber and stablizes flow velocity, gas injection direction becomes 30 ~ 60 ° with graphite flake surface and is ejected on graphite flake, the pulse laser focused on through convergent lens excites generation plasma to gas eject position irradiation on meta anthracite and launches spectral signal, spectrometer with ICCD carries out light splitting and detection to the light signal collected.
5. direct-current discharge vaporization auxiliary laser induced breakdown spectroscopy detects the device of trace metal element in water body according to claim 2, it is characterized in that, the internal diameter of the interior pipe of described gas-liquid separation device is 2 ~ 3mm, thick 2 ~ 4mm, outer tube diameter is 10 ~ 20mm, external diameter is 20mm, and whole device length is 200 ~ 400mm.
6. direct-current discharge gasification auxiliary laser induced breakdown spectroscopy detects the device of trace metal element in water body according to claim 2, it is characterized in that, described gas buffer room is connected with gas-liquid separator wireway, there are two wireways gas buffer room, wherein draft tube is passed into position at the bottom of bottle, the escape pipe mouth of pipe is near bottleneck, and wireway internal diameter is 5 ~ 10mm, and snubber assembly makes gaseous sample flow speed stability.
7. direct-current discharge vaporization auxiliary laser induced breakdown spectroscopy detects the device of trace metal element in water body according to claim 2, it is characterized in that, described pulsed laser is Nd:YAG pulsed laser, laser output wavelength is 1064nm, 532nm or 266nm, pulsed laser energy is 10mJ ~ 100mJ.
8. direct-current discharge vaporization auxiliary laser induced breakdown spectroscopy detects the device of trace metal element in water body according to claim 2, it is characterized in that, gas nozzle internal diameter size is in 0.2 ~ 2mm scope, and the angle of gas injection direction and graphite surface is 30 ~ 60 °.
9. direct-current discharge vaporization auxiliary laser induced breakdown spectroscopy detects the device of trace metal element in water body according to claim 2, and it is characterized in that, laser pulse active position is ejected into graphite place-centric at gas.
10. direct-current discharge vaporization auxiliary laser induced breakdown spectroscopy detects the device of trace metal element in water body according to claim 2, it is characterized in that, described spectrometer comprises ICCD, and ICCD time delay is selected in 200ns ~ 2000ns scope, and ICCD gate-width is selected between 1 μ s ~ 50 μ s.
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